JP2018052112A - Multilayer film for fiber bonding and/or fiber sheet surface protection, and thermosetting composition for fiber bonding and/or fiber sheet surface protection - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multilayer film for fiber bonding and/or fiber sheet surface protection, which has excellent fiber impregnability, a shortened curing time, and excellent productivity and workability.SOLUTION: The present invention relates to a multilayer film for fiber bonding and/or fiber sheet surface protection, which is obtained by laminating a layer (I) that is formed from a thermosetting composition (i) on a support film (II), and wherein the thermosetting composition (i) contains a thermal polymerization initiator (C) that has a 10-hour half-life temperature of 65°C or higher.SELECTED DRAWING: None

Description

  The present invention relates to a thermosetting composition for fiber bonding and / or fiber sheet surface protection, and more specifically, used for bonding fibers of carbon fibers, glass fibers, and the like, and protecting the surface of a fiber sheet composed of such fibers. It relates to the thermosetting composition obtained.

Fiber reinforced plastic is a composite material that is made of carbon fiber, glass fiber, or other fiber as a reinforcing material and improved in strength, and is used as a material that is lightweight and strong, that is, has a high specific strength. . Such fiber reinforced plastics have been used in sports equipment, aircraft, and artificial satellites because of their excellent mechanical properties, but in the future, they are expected to be expanded to the automotive field due to the expectation of improved fuel economy due to weight reduction. Yes.
Among the fiber reinforced plastics, for example, carbon fibers in carbon fiber reinforced plastics are required to be lightweight, high in strength, and impregnated with resin. Carbon fiber reinforced plastics are moldable, productive (shortening curing time, workability), and recycled. Performance and shape stability are required.

For the production of carbon fiber reinforced plastics, for example, a prepreg method using a prepreg that is a sheet-like intermediate base material in which carbon fiber is impregnated with an uncured resin is used. In this prepreg method, after a plurality of prepregs are laminated, An uncured resin is cured to produce a carbon fiber reinforced plastic.
Examples of such resins include thermoplastic resins and thermosetting resins. However, when a thermoplastic resin is used, a high molecular weight resin is used to maintain an appropriate strength, resulting in an increase in viscosity. There is a problem that it is difficult to impregnate carbon fibers, and there is a problem in terms of high strength.
On the other hand, for example, a thermosetting resin such as a thermosetting resin epoxy disclosed in Patent Document 1 is easily impregnated into carbon fibers, but it takes a long time to cure, and there are problems in productivity and workability.

JP 2003-201388 A

  Therefore, in the present invention, under such a background, a fiber adhesion and / or fiber sheet surface protective laminate that has good impregnation into fibers, can shorten the curing time, and has good productivity and workability. The object is to provide a film and a thermosetting composition for fiber adhesion and / or fiber sheet surface protection.

  However, the present inventors have conducted intensive research in view of such circumstances, and as a result, by using a thermosetting composition containing a thermopolymerization initiator having a high 10-hour half-life temperature, the thermosetting composition can be obtained. The present invention has been completed by finding that the fibers can be easily impregnated and the curing time can be shortened.

  That is, the gist of the present invention is a laminated film for fiber adhesion and / or fiber sheet surface protection in which a layer [I] composed of a thermosetting composition [i] and a support film [II] are laminated. The thermosetting composition [i] contains a thermal polymerization initiator (C) having a 10-hour half-life temperature of 65 ° C. or higher, and is a laminated film for fiber adhesion and / or fiber sheet surface protection It is about.

  Further, the gist of the present invention includes a binder polymer (A), a reactive oligomer (B) having one or more unsaturated groups, and a thermal polymerization initiator (C) having a 10-hour half-life temperature of 65 ° C. or higher. The present invention also relates to a thermosetting composition for fiber adhesion and / or fiber sheet surface protection.

In the laminated film for fiber adhesion and / or fiber sheet surface protection of the present invention, since the thermosetting composition [i] contains a thermal polymerization initiator having a high 10-hour half-life temperature, the thermosetting composition [ i] has a relatively low viscosity in the melting process and is easily impregnated into the fiber. Therefore, the polymerization is started and thermoset as the temperature rises due to heating, so that the adhesiveness between the thermosetting composition [i] and the fibers is improved, the adhesiveness between the fibers and the surface smoothness of the fiber sheet, Excellent design such as gloss.
In addition, in the prepreg method, after the layer [I] made of the thermosetting composition [i] laminated on the support film [II] is laminated on the fiber sheet made of fibers, the thermosetting composition is obtained by hot pressing or the like. By impregnating [i] into a fiber sheet and thermosetting it, a fiber-reinforced plastic can be produced in a short time, so that productivity and workability are excellent.

  Furthermore, the thermosetting composition for fiber bonding and / or fiber sheet surface protection of the present invention can only be a composition constituting layer [I] in the laminated film for fiber bonding and / or fiber sheet surface protection of the present invention. Not only in RTM (resin injection molding) method, hand lay-up molding method, SMC press molding method, BMC molding method, FW (filament winding) method, pultrusion molding method, pin winding molding method, etc. It can be utilized, and has the effect of being excellent in design properties such as adhesion between fibers, surface smoothness of fiber reinforced plastic, and glossiness.

  Hereinafter, although it demonstrates in detail about the structure of this invention, these show an example of a desirable embodiment, and this invention is not specified by these content.

The laminated film of the present invention is a laminated film for fiber adhesion and / or fiber sheet surface protection in which a layer [I] composed of a thermosetting composition [i] and a support film [II] are laminated.
Hereinafter, the thermosetting composition [i] will be described.
Hereinafter, the laminated film for fiber adhesion and / or fiber sheet surface protection of the present invention may be simply abbreviated as “laminated film”, and the cured thermosetting composition [i] is referred to as “cured product [i]”. The layer [I] composed of the uncured thermosetting composition [i] may be referred to as the “thermosetting composition layer [I]”, and the thermosetting composition after curing. The layer [I] composed of [i] may be referred to as “cured layer [I]”.

The thermosetting composition [i] used in the present invention is a resin composition that can be cured by heat, and preferably contains a compound having an unsaturated group. Examples of the compound having an unsaturated group include reactive oligomers and reactive monomers having one or more unsaturated groups.
More preferably, the thermosetting composition [i] is a binder polymer (A), a reactive oligomer (B) having one or more unsaturated groups, and a thermal polymerization initiator having a 10-hour half-life temperature of 65 ° C. or higher ( C) is a thermosetting composition for fiber adhesion and / or fiber sheet surface protection of the present invention.
Hereinafter, each component will be described.

<Binder polymer (A)>
The binder polymer (A) in the present invention is used for the purpose of adjusting the viscosity of the uncured thermosetting composition [i]. For example, a (meth) acrylic resin, a polyurethane resin, and an epoxy resin are used. Etc. Among these, (meth) acrylic resin (A1) is preferable in terms of facilitating the adjustment of the viscosity.
Hereinafter, the (meth) acrylic resin (A1) will be described more specifically.
In addition, (meth) acryl represents acryl or methacryl, and (meth) acrylate represents acrylate or methacrylate.

[(Meth) acrylic resin (A1)]
The (meth) acrylic resin (A1) in the present invention is obtained by polymerizing a monomer component containing a (meth) acrylic monomer. (Meth) acrylic-type resin (A1) can be used individually by 1 type or in combination of 2 or more types.

The (meth) acrylic resin (A1) preferably contains the (meth) acrylic acid ester monomer (a1) as the main polymerization component, and if necessary, the functional group-containing monomer (a2) and other copolymers. The polymerizable monomer (a3) can also be used as a copolymerization component.
Examples of the (meth) acrylic acid ester monomer (a1) include, for example, aliphatic (meth) acrylic acid ester monomers such as (meth) acrylic acid alkyl ester, and aromatic monomers such as (meth) acrylic acid phenyl ester. Examples include (meth) acrylic acid ester monomers.

For such (meth) acrylic acid alkyl ester, the alkyl group usually has 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. Specifically, for example, methyl (meta) ) Acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-propyl (meth) acrylate, n-hexyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate Etc. Examples of the (meth) acrylic acid phenyl ester include benzyl (meth) acrylate and phenoxyethyl (meth) acrylate.
Examples of other (meth) acrylic acid ester monomers (a1) include tetrahydrofurfuryl (meth) acrylate. These can be used alone or in combination of two or more.

  Among these (meth) acrylic acid ester monomers (a1), methyl (meth) acrylate, n-butyl (meth) acrylate, 2 in terms of copolymerizability, adhesive physical properties, ease of handling and availability of raw materials. -Ethylhexyl (meth) acrylate is preferably used.

  Examples of the functional group-containing monomer (a2) include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an alkoxy group-containing monomer, a phenoxy group-containing monomer, an amide group-containing monomer, an amino group-containing monomer, other nitrogen-containing monomers, and a glycidyl group-containing Monomers, phosphoric acid group-containing monomers, sulfonic acid group-containing monomers and the like can be mentioned, and these can be used alone or in combination of two or more.

  Examples of the hydroxyl group-containing monomer include a primary hydroxyl group-containing monomer, a secondary hydroxyl group-containing monomer, and a tertiary hydroxyl group-containing monomer. Examples of the primary hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 8-hydroxyoctyl. (Meth) acrylic acid hydroxyalkyl ester containing primary hydroxyl group such as (meth) acrylate, 10-hydroxydecyl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate; caprolactone-modified 2-hydroxyethyl Caprolactone-modified monomers such as (meth) acrylate; 2-acryloyloxyethyl-2-hydroxyethylphthalic acid; N-methylol (meth) acrylamide; N-hydroxyethyl (meth) acrylamide It is. Examples of the secondary hydroxyl group-containing monomer include secondary hydroxyl group-containing (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxypropyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate; 2-hydroxy-3-phenoxy Examples include propyl (meth) acrylate; 3-chloro-2-hydroxypropyl (meth) acrylate; 2-hydroxy-3-phenoxypropyl (meth) acrylate. Examples of the tertiary hydroxyl group-containing monomer include 2,2-dimethyl-2-hydroxyethyl (meth) acrylate.

  Examples of the hydroxyl group-containing monomer include polyethylene glycol derivatives such as diethylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate, polypropylene glycol derivatives such as polypropylene glycol mono (meth) acrylate, and polyethylene glycol-polypropylene glycol-mono. Oxyalkylene-modified monomers such as (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, and poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate may be used.

  Examples of the carboxyl group-containing monomer include Michael addition of acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, acrylamide N-glycolic acid, cinnamic acid, and (meth) acrylic acid. (Eg, acrylic acid dimer, methacrylic acid dimer, acrylic acid trimer, methacrylic acid trimer, acrylic acid tetramer, methacrylic acid tetramer, etc.), 2- (meth) acryloyloxyethyl dicarboxylic acid monoester (eg, 2-acryloyloxyethyl) Succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, 2-acryloyloxyethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahi Rofutaru acid monoester, 2-methacryloyloxyethyl hexahydrophthalic acid mono ester) and the like. Such a carboxyl group-containing monomer may be used as an acid, or may be used in the form of a salt neutralized with an alkali.

  Examples of the alkoxy group-containing monomer include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, and 2-butoxydiethylene glycol. (Meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, octoxypolyethylene glycol- Polypropylene glycol-mono (meth) acrylate, lauroxypolyethylene glycol mono (meth) acrylate, steer Aliphatic (meth) acrylic acid esters such as xypolyethylene glycol mono (meth) acrylate and the like. Examples of the phenoxy group-containing monomer include 2-phenoxyethyl (meth) acrylate and phenoxypolyethylene glycol (meth) acrylate. And acrylate esters of aromatic (meth) acrylates such as phenoxypolyethylene glycol-polypropylene glycol (meth) acrylate and nonylphenol ethylene oxide adduct (meth) acrylate.

  Examples of the amide group-containing monomer include acrylamide, methacrylamide, N- (n-butoxyalkyl) acrylamide, N- (n-butoxyalkyl) methacrylamide, N, N-dimethyl (meth) acrylamide, N, N- Examples include diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, acrylamide-3-methylbutylmethylamine, dimethylaminoalkylacrylamide, and dimethylaminoalkylmethacrylamide.

Examples of the amino group-containing monomer include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and a quaternized product thereof.
Examples of the nitrogen-containing monomer other than the amide group-containing monomer and the amino group-containing monomer include acryloylmorpholine.

  Examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate and allyl glycidyl ether.

  Examples of the phosphoric acid group-containing monomer include 2- (meth) acryloyloxyethyl acid phosphate, bis (2- (meth) acryloyloxyethyl) acid phosphate, and the like.

  Examples of the sulfonic acid group-containing monomer include olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid, and methallyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, styrene sulfonic acid, and salts thereof. .

  Examples of other copolymerizable monomers (a3) include acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyl toluene, Examples include vinyl pyridine, vinyl pyrrolidone, itaconic acid dialkyl ester, fumaric acid dialkyl ester, allyl alcohol, acrylic chloride, methyl vinyl ketone, N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, and dimethylallyl vinylketone.

  For the purpose of increasing the molecular weight, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate A compound having two or more ethylenically unsaturated groups such as divinylbenzene can also be used in combination.

  In (meth) acrylic resin (A1), the content ratio of (meth) acrylic acid ester monomer (a1), functional group-containing monomer (a2), and other copolymerizable monomer (a3) is (meth) acrylic acid. The ester monomer (a1) is preferably 10 to 100% by weight, particularly preferably 20 to 95% by weight, and the functional group-containing monomer (a2) is preferably 0 to 90% by weight, particularly preferably 5 to 80% by weight. The other copolymerizable monomer (a3) is preferably 0 to 50% by weight, particularly preferably 5 to 40% by weight.

  In the present invention, the (meth) acrylic resin (A1) is cured in terms of excellent compatibility with a urethane (meth) acrylate compound suitable as a reactive oligomer (B) having one or more unsaturated groups. From the viewpoint of adjusting the hardness of the product [i], a polymer having methyl (meth) acrylate as a polymerization component is preferable, and a polymer having methyl methacrylate as a polymerization component is particularly preferable. Polymethyl methacrylate is preferred.

  In the present invention, the (meth) acrylic resin (A1) can be produced by polymerizing the monomer components (a1) to (a3). Such polymerization can be performed by a conventionally known method such as solution radical polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization. For example, in an organic solvent, a polymerization monomer such as the above (meth) acrylic acid ester monomer (a1), functional group-containing monomer (a2), other copolymerizable monomer (a3), polymerization initiator (azobisisobutyrate) Ronitrile, azobisisovaleronitrile, benzoyl peroxide, etc.) are mixed or dropped and polymerized at reflux or at 50 to 90 ° C. for 2 to 20 hours.

  Examples of the organic solvent used in the polymerization reaction include aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane; esters such as ethyl acetate and butyl acetate; n-propyl alcohol and isopropyl alcohol. Aliphatic alcohols such as acetone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and the like.

  The glass transition temperature (Tg) of the (meth) acrylic resin (A1) is usually 40 to 120 ° C., preferably 60 to 110 ° C. If the glass transition temperature is too high, the amount of the (meth) acrylic resin (A1) that can be blended in preparing the thermosetting composition [i] is limited, and the uncured thermosetting composition [i] The viscosity adjustment range is narrowed, and as a result, the durability of the cured product [i] tends to decrease or the strength tends to decrease due to being too hard, and if the glass transition temperature is too low, the thermal durability of the cured product [i] is reduced. There is a tendency to decrease.

The glass transition temperature (Tg) is calculated from the following Fox equation.
1 / Tg = w1 / Tg1 + w2 / Tg2 + ... Wk / Tgk
Where Tg is the glass transition temperature of the copolymer, Tg1, Tg2,... Tgk is the Tg of the homopolymer of each monomer component, w1, w2,. ... Wk represents the molar fraction of each monomer component, and w1 + w2 +... Wk = 1.

The weight average molecular weight of the (meth) acrylic resin (A1) thus obtained is usually 10,000 to 3,000,000, preferably 20,000 to 2,500,000.
If the weight average molecular weight is too small, the uncured thermosetting composition [i] becomes soft, and the tackiness becomes higher than necessary, and the handling property tends to be lowered. Further, the cured product [i] Tend to be brittle. If the weight average molecular weight is too large, the viscosity of the thermosetting composition [i] before coating on the support film [II] becomes too high, or it becomes difficult to increase the concentration. There is a tendency to cause a decrease in workability, and further, the flexibility of the thermosetting composition layer [I] before curing is lowered, making it difficult to wind the laminated film of the present invention into a roll shape, etc. Tend.
In addition, said weight average molecular weight is based on standard polystyrene molecular weight conversion, column: Shodex GPC KF in high performance liquid chromatography (The Japan Waters company make, "Waters2695 (main body)" and "Waters2414 (detector)"). −806 L (exclusion limit molecular weight: 2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theoretical plate number: 10,000 plates / piece, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 μm ) Can be used for measurement.

<Reactive oligomer (B) having one or more unsaturated groups>
Examples of the reactive oligomer (B) having one or more unsaturated groups in the present invention include urethane (meth) acrylate compounds (B1), epoxy (meth) acrylate compounds, polyester (meth) acrylate compounds, and the like. Can be mentioned. Among these, the urethane (meth) acrylate compound (B1) is preferable from the viewpoint of imparting appropriate elasticity to the cured layer [I].
Hereinafter, the urethane (meth) acrylate compound (B1) will be described more specifically.

[Urethane (meth) acrylate compound (B1)]
As the urethane (meth) acrylate compound (B1) used in the present invention, for example, a hydroxyl group-containing (meth) acrylate compound (b1), a polyvalent isocyanate compound (b2), and a polyol compound (b3) are reacted. The urethane (meth) acrylate type compound (B1) obtained is mentioned.

  The weight average molecular weight of the urethane (meth) acrylate compound (B1) used in the present invention is preferably 500 to 50000, and particularly preferably 1000 to 30000. When the weight average molecular weight is too small, the cured layer [I] tends to be brittle, and when it is too large, the cured layer [I] becomes too hard and impact resistance tends to be lowered.

In addition, said weight average molecular weight is a weight average molecular weight by standard polystyrene molecular weight conversion, column: Shodex GPC KF-806L (exclusion) in a high performance liquid chromatography (Showa Denko Co., Ltd. make, "Shodex GPC system-11 type | mold"). Limit molecular weight: 2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theoretical plate number: 10,000 plate / piece, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 μm) It can be measured by using a series.

The urethane (meth) acrylate compound (B1) has a viscosity at 60 ° C. of preferably 500 to 150,000 mPa · s, particularly preferably 500 to 120,000 mPa · s, and still more preferably 1,000 to 100,000 mPa. -S. When the viscosity is outside the above range, the coating property when applying the thermosetting composition [i] to the support film [II] tends to be lowered.
The viscosity can be measured with an E-type viscometer.

[Hydroxyl-containing (meth) acrylate compound (b1)]
Examples of the hydroxyl group-containing (meth) acrylate compound (b1) include hydroxyalkyl (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth)). Acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, etc.), 2-hydroxyethylacryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxy Ethyl (meth) acrylate, dipropylene glycol (meth) acrylate, fatty acid-modified glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol (Meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyl-oxypropyl methacrylate, pentaerythritol tri (meth) acrylate , Caprolactone modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol penta ( And (meth) acrylate.

Among these, a hydroxyl group (meth) acrylate compound having one ethylenically unsaturated group is preferable because it can reduce curing shrinkage during the formation of the cured layer [I], and particularly preferably 2-hydroxy Hydroxyalkyl (meth) acrylates such as ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, etc. In addition, it is preferable to use 2-hydroxyethyl (meth) acrylate in terms of excellent reactivity and versatility.
Moreover, these can be used individually by 1 type or in combination of 2 or more types.

[Polyisocyanate compound (b2)]
Examples of the polyvalent isocyanate compound (b2) include aromatics such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate. Polyisocyanates; aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate; hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (Isocyanatomethyl) Alicyclic polyisocyanates such as hexane; or trimer compounds or multimeric compounds of these polyisocyanates; allophanate polyisocyanates; burette polyisocyanates; water-dispersed polyisocyanates (for example, manufactured by Nippon Polyurethane Industry Co., Ltd.) "Aquanate 100", "Aquanate 110", "Aquanate 200", "Aquanate 210", etc.);

  Among these, aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate; hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1, An alicyclic diisocyanate such as 3-bis (isocyanatomethyl) cyclohexane is preferably used, and isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate is particularly preferably used in terms of low curing shrinkage, and further Preferably, isophorone diisocyanate is used in terms of excellent reactivity and versatility.

[Polyol compound (b3)]
Examples of the polyol compound (b3) include polyether glycol, polyester polyol, polycarbonate polyol, polyolefin polyol, polybutadiene polyol, (meth) acrylic polyol, polysiloxane polyol, and the like. And alkylene glycols such as propylene glycol and neopentyl glycol.

  Examples of the polyether polyol include, for example, polyether glycols containing an alkylene structure such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, and polyhexamethylene glycol, and random or block copolymers of these polyalkylene glycols. Examples include coalescence.

  Examples of the polyester-based polyol include three types of components: a condensation polymer of a polyhydric alcohol and a polycarboxylic acid; a ring-opening polymer of a cyclic ester (lactone); a polyhydric alcohol, a polycarboxylic acid, and a cyclic ester. And the like.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1,3-tetramethylene diol, 2-methyl-1,3-trimethyl. Methylene diol, 1,5-pentamethylene diol, neopentyl glycol, 1,6-hexamethylene diol, 3-methyl-1,5-pentamethylene diol, 2,4-diethyl-1,5-pentamethylene diol, glycerin , Trimethylolpropane, trimethylolethane, cyclohexanediols (such as 1,4-cyclohexanediol), bisphenols (such as bisphenol A), and sugar alcohols (such as xylitol and sorbitol).

  Examples of the polyvalent carboxylic acid include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; -Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid, trimellitic acid, and the like.

  Examples of the cyclic ester include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone.

  Examples of the polycarbonate-based polyol include a reaction product of a polyhydric alcohol and phosgene; a ring-opening polymer of a cyclic carbonate (such as alkylene carbonate).

  Examples of the polyhydric alcohol include polyhydric alcohols exemplified in the description of the polyester-based polyol, and examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, and the like. It is done.

  In addition, the polycarbonate polyol should just be a compound which has a carbonate bond in a molecule | numerator, and the terminal is a hydroxyl group, and may have an ester bond with a carbonate bond.

  Examples of the polyolefin-based polyol include those having a homopolymer or copolymer such as ethylene, propylene, and butene as a saturated hydrocarbon skeleton, and having a hydroxyl group at the molecular end.

Examples of the polybutadiene-based polyol include those having a butadiene copolymer as a hydrocarbon skeleton and having a hydroxyl group at the molecular end.
The polybutadiene-based polyol may be a hydrogenated polybutadiene polyol in which all or part of the ethylenically unsaturated groups contained in the structure thereof are hydrogenated.

  Examples of the (meth) acrylic polyol include those having at least two hydroxyl groups in the molecule of the polymer or copolymer of the (meth) acrylic acid ester. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid alkyl esters such as 2-ethylhexyl acid, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, and the like.

  Examples of the polysiloxane-based polyol include dimethyl polysiloxane polyol and methylphenyl polysiloxane polyol.

  Among these, polyester-based polyols and polyether-based polyols are preferable, and polyester-based polyols are particularly preferable because they are excellent in mechanical properties such as flexibility during curing.

  As a weight average molecular weight of the said polyol type compound (b3), 500-8000 are preferable, Especially preferably, it is 550-5000, More preferably, it is 600-3000. If the molecular weight of the polyol compound (b3) is too large, the mechanical properties of the cured layer [I] tend to decrease during curing, and if it is too small, the shrinkage of curing tends to increase and the stability tends to decrease.

In addition, said weight average molecular weight is a weight average molecular weight by standard polystyrene molecular weight conversion, column: Shodex GPC KF-806L (exclusion) in a high performance liquid chromatography (Showa Denko Co., Ltd. make, "Shodex GPC system-11 type | mold"). Limit molecular weight: 2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theoretical plate number: 10,000 plate / piece, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 μm) It can be measured by using a series.

  The urethane (meth) acrylate compound (B1) is usually the above hydroxyl group-containing (meth) acrylate compound (b1), polyisocyanate compound (b2), and polyol compound (b3) in a reactor or separately. It can be manufactured by charging and reacting. Further, the reaction product obtained by reacting the polyol compound (b3) and the polyvalent isocyanate compound (b2) in advance is reacted with the hydroxyl group-containing (meth) acrylate compound (b1) to obtain urethane (meth) acrylate. The compound (B1) can also be produced, and this production method is useful in terms of reaction stability, reduction of byproducts, and the like.

  For the reaction between the polyol compound (b3) and the polyvalent isocyanate compound (b2), known reaction means can be used. In that case, for example, the molar ratio of the isocyanate group in the polyvalent isocyanate compound (b3) to the hydroxyl group in the polyol compound (b3) is usually about 2n: (2n-2) (n is an integer of 2 or more). By doing this, after obtaining a terminal isocyanate group-containing urethane (meth) acrylate compound having an isocyanate group remaining, an addition reaction with the hydroxyl group-containing (meth) acrylate compound (b1) becomes possible.

  The addition reaction of the reaction product obtained by reacting the polyol compound (b3) and the polyvalent isocyanate compound (b2) in advance with the hydroxyl group-containing (meth) acrylate compound (b1) is also a known reaction. Means can be used.

  The reaction molar ratio of the reaction product to the hydroxyl group-containing (meth) acrylate compound (b1) is, for example, that the polyisocyanate compound (b2) has two isocyanate groups and the hydroxyl group-containing (meth) acrylate compound (b1). ) Has one hydroxyl group, the reaction product: hydroxyl group-containing (meth) acrylate compound (b1) is about 1: 2, and the polyisocyanate compound (b2) has three isocyanate groups. When the hydroxyl group-containing (meth) acrylate compound (b1) has one hydroxyl group, the reaction product: hydroxyl group-containing (meth) acrylate compound (b1) is about 1: 3.

  In the addition reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (b1), the reaction is terminated when the residual isocyanate group content in the reaction system is 0.5% by weight or less. A (meth) acrylate compound (B1) is obtained.

  In the reaction between the polyol compound (b3) and the polyvalent isocyanate compound (b2), and further in the reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (b1), a catalyst is used for the purpose of promoting the reaction. It is also preferable to use. Examples of such catalysts include organometallic compounds such as dibutyltin dilaurate, trimethyltin hydroxide, and tetra-n-butyltin; zinc octoate, tin octoate, cobalt naphthenate, stannous chloride, stannic chloride, and the like. Metal salt of triethylamine, benzyldiethylamine, 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] undecene, N, N, N ′, N′-tetramethyl- Amine-based catalysts such as 1,3-butanediamine and N-ethylmorpholine; inorganic bismuth compounds such as bismuth nitrate, bismuth bromide, bismuth iodide and bismuth sulfide, and organic bismuth compounds such as dibutyl bismuth dilaurate and dioctyl bismuth dilaurate And; bismuth 2-ethylhexanoate, bismuth naphthenate, isodeca Bismuth acid salt, bismuth neodecanoate, bismuth laurate, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth bisneodecanoate, bismuth disalicylate, Bismuth-based catalysts such as organic acid bismuth salts such as bismuth digallate; among others, dibutyltin dilaurate and 1,8-diazabicyclo [5,4,0] undecene are preferred.

  In the reaction between the polyol compound (b3) and the polyvalent isocyanate compound (b2), and further in the reaction between the reaction product and the hydroxyl group-containing (meth) acrylate compound (b1), it reacts with the isocyanate group. Organic solvents having no functional group, for example, esters such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic solvents such as toluene and xylene; and the like can be used.

  Moreover, reaction temperature is 30-90 degreeC normally, Preferably it is 40-80 degreeC, and reaction time is 2 to 10 hours normally, Preferably it is 3 to 8 hours.

The urethane (meth) acrylate compound (B1) used in the present invention is preferably one having 20 or less ethylenically unsaturated groups, particularly preferably 10 in view of taking advantage of adhesion to fibers. Those having the following ethylenically unsaturated groups, more preferably those having 5 or less ethylenically unsaturated groups. The lower limit of the number of ethylenically unsaturated groups is usually 2.

  The content ratio (weight ratio) of the binder polymer (A) and the reactive oligomer (B) having one or more unsaturated groups is usually binder polymer (A): reactive oligomer (B) = 90: 10-10. : 90, preferably 70:30 to 20:80, particularly preferably 60:40 to 30:70. If the amount of the binder polymer (A) is too small (there are too many reactive oligomers (B)), the surface of the cured layer [I] after curing will exhibit tackiness, which will hinder subsequent processes and the cured layer [ I] tends to cause curing shrinkage and cause cracks in the cured layer [I]. If the binder polymer (A) is too much (the reactive oligomer (B) is too little), the thermosetting composition The material layer [I] becomes too hard, and the thermosetting composition layer [I] is cracked by the handling of the laminated film of the present invention, and the laminated film of the present invention is applied to a fiber layer such as a fiber sheet. There is a tendency that followability and the like at the time of lamination also decrease.

<Thermal polymerization initiator (C)>
The thermal polymerization initiator (C) in the present invention has an important 10-hour half-life temperature of 65 ° C. or higher, preferably 70 to 200 ° C., particularly preferably 75 to 170 ° C., more preferably 80 to 150. ° C. If the half-life temperature is too low, the thermosetting composition [i] is cured before melting, does not penetrate into the fibers, and sufficient adhesion cannot be obtained, or surface smoothness can be obtained. There is a tendency to not.

Examples of the thermal polymerization initiator (C) include an azobis compound having a 10-hour half temperature of 65 ° C. or higher and a peroxide compound having a 10 hour half temperature of 65 ° C. or higher.
Examples of azobis compounds having a 10-hour half-life temperature of 65 ° C. or more include 2,2′-azobisisobutyronitrile (65 ° C.), 2,2′-azobis (2-methylbutyronitrile) (66 ° C.). ), Dimethyl-2,2′-azobisisoobtyrate (66 ° C.), 1,1′-azobis (cyclohexane-1-carbonitrile) (88 ° C.), and the like.
Examples of peroxide compounds having a 10-hour half-life temperature of 65 ° C. or higher include 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane (66.2 ° C.), t-hexylperoxy. 2-ethylhexanoate (69.9 ° C), di (4-methylbenzoyl) peroxide (70.6 ° C), t-butylperoxy-2-ethylhexanoate, (72.1 ° C), benzoyl par Oxide (73.6 ° C), 1,1'-di (t-hexylperoxy) cyclohexane (87.1 ° C), 1,1-di (t-butylperoxy) cyclohexane (90.7 ° C), t-hexyl Peroxyisopropyl monocarbonate (95.0 ° C), t-butylperoxymalonic acid (96.1 ° C), t-butylperoxylaurate (98.3 ° C), t- Xylperoxybenzoate (99.4 ° C), t-butylperoxyacetate (101.9 ° C), t-butylbenzoyl peroxide (104.3 ° C), dicumyl peroxide (116.4 ° C), t-butylcumyl peroxide (119.5 ° C), di-t-butyl peroxide (123.7 ° C), diisopropylbenzene hydroperoxide (128.0 ° C), diisopropylbenzene hydroperoxide (145.1 ° C), cumene hydroperoxide (157.9 ° C) ) Peroxide compounds such as t-butyl hydroperoxide (166.5 ° C.).
These compounds can be used alone or in combination of two or more.
In addition, the temperature written together with said each compound is a 10-hour half-life temperature.

Among them, a peroxide compound is preferable in that a gas generated during curing is small. Specifically, for example, 1,1′-di (t-hexylperoxy) cyclohexane (87.1 ° C.), 1, 1-di (t-butylperoxy) cyclohexane (90.7 ° C), t-hexylperoxyisopropyl monocarbonate (95.0 ° C), t-butylperoxymalonic acid (96.1 ° C), t-butylperoxylaur Rate (98.3 ° C), t-hexylperoxybenzoate (99.4 ° C), t-butylberoxyacetate (101.9 ° C), t-butylbenzoyl peroxide (104.3 ° C), dicumyl peroxide (116 4 ° C), t-butylcumyl peroxide (119.5 ° C), di-t-butyl peroxide (123.7 ° C), diisopropyl Pills benzene hydroperoxide (128.0 ° C.), diisopropylbenzene hydroperoxide (145.1 ° C.) are preferred.
It is.

  These auxiliary agents include triethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone (Michler ketone), 4,4′-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoic acid. Ethyl, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone Etc. can be used in combination.

The content of the thermal polymerization initiator (C) in the thermosetting composition [i] is the total non-volatile content of the binder polymer (A) component, the reactive oligomer (B) component, and the reactive monomer (D) component described later. Is preferably 0.1 to 30 parts by weight, particularly preferably 0.5 to 20 parts by weight, and still more preferably 1 to 10 parts by weight.
If the content of the thermal polymerization initiator (C) is too small, the cured layer [I] is insufficiently cured and sufficient elasticity or hardness cannot be obtained, and the cured layer [I] tends to become brittle and cannot function. If the content is too large, the thermal polymerization initiator (C) bleeds out during storage of the thermosetting composition layer [I], and crystals tend to precipitate in the cured layer [I]. is there.

<Reactive monomer (D) having one or more unsaturated groups>
The thermosetting composition [i] in the present invention preferably further contains a reactive monomer (D) having one or more unsaturated groups.
As the reactive monomer (D) having one or more unsaturated groups, for example, a monofunctional monomer, a bifunctional monomer, a trifunctional or higher monomer, other ethylenically unsaturated monomers, and the like can be used.

  As the monofunctional monomer, a monomer containing one ethylenically unsaturated group is used. For example, styrene, vinyl toluene, chlorostyrene, α-methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, acrylonitrile. , Vinyl acetate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate Rate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate , Octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, n-stearyl (meth) acrylate, benzyl (meth) acrylate, phenol ethylene oxide modified ( Phthalic acid derivatives such as (meth) acrylate, nonylphenol propylene oxide modified (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate -Furester (meth) acrylate, furfuryl (meth) acrylate, carbitol (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, allyl (meth) acrylate, acryloylmorpholine, 2-hydroxyethylacrylamide, N- Examples include methylol (meth) acrylamide, N-vinylpyrrolidone, 2-vinylpyridine, 2- (meth) acryloyloxyethyl acid phosphate monoester and the like.

  As the bifunctional monomer, a monomer containing two ethylenically unsaturated groups is used. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol Di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide Modified bisphenol A type di (meth) acrylate, propylene oxide modified bisphenol A type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate 1,6-hexanediol ethylene oxide modified di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) ) Acrylate, diglycidyl phthalate di (meth) acrylate, hydroxypivalic acid-modified neopentyl glycol di (meth) acrylate, isocyanuric acid ethylene oxide-modified diacrylate, 2- (meth) acryloyloxyethyl acid phosphate diester, etc. .

  As the trifunctional or higher functional monomer, a monomer containing three or more ethylenically unsaturated groups is used. For example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) Acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, glycerin Polyglycidyl ether poly (meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate, ethylene oxide modified dipentaerythritol pen (Meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tetra (meth) acrylate, succinic acid modified pentaerythritol tri (meth) acrylate Etc.

  Examples of the other ethylenically unsaturated monomers include, in addition to the above, a Michael adduct of acrylic acid or 2-acryloyloxyethyl dicarboxylic acid monoester. Examples of the Michael adduct of acrylic acid include acrylic acid dimer, methacrylic acid Examples include acid dimers, acrylic acid trimers, methacrylic acid trimers, acrylic acid tetramers, and methacrylic acid tetramers. Examples of the 2-acryloyloxyethyl dicarboxylic acid monoester which is a carboxylic acid having a specific substituent include, for example, 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, and 2-acryloyl. Examples thereof include oxyethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, and 2-methacryloyloxyethyl hexahydrophthalic acid monoester. Furthermore, oligoester acrylate is also mentioned.

  The reactive monomer (D) having one or more unsaturated groups in the present invention is preferably a bifunctional monomer or a polyfunctional monomer of a trifunctional or higher monomer, and particularly preferably as the above bifunctional monomer or a trifunctional or higher functional monomer. It is the polyfunctional (meth) acrylate compound (D1) mentioned.

The content of the reactive monomer (D) in the thermosetting composition [i] is 1 to 2 when the total nonvolatile content of the binder polymer (A) component and the reactive oligomer (B) component is 100 parts by weight. The amount is preferably 100 parts by weight, particularly preferably 3 to 80 parts by weight, and further preferably 5 to 70 parts by weight.
If the content of the reactive monomer (D) is too small, the flexibility of the thermosetting composition layer [I] tends to decrease and the processability tends to decrease, and if it is too large, the cured layer [I] becomes hard. Too much, impact resistance tends to decrease and become brittle.

  In the thermosetting composition [i] in the present invention, a plasticizer, an antioxidant, a solvent, a surface tension modifier, a stabilizer, a chain transfer agent, a surfactant and the like are known as necessary. Additives may be added.

<Laminated film for fiber adhesion and / or fiber sheet surface protection>
The laminated film for fiber adhesion and / or fiber sheet surface protection of the present invention has a structure in which a layer [I] composed of a thermosetting composition [i] and a support film [II] are laminated.

Examples of the support film [II] include a polyethylene terephthalate (PET) film, a release PET film, a polypropylene film, a polyethylene film, a polyethylene naphthalate film, a polyvinyl alcohol film, an ethylene vinyl alcohol copolymer film, or a resin layer. It is preferable to use paper or the like laminated on the surface.
Among these, in view of heat resistance at the time of film formation and curing of the thermosetting composition layer [I], a PET film, a release PET film subjected to a release treatment, or a paper having a resin layer laminated on the surface ( Hereinafter, it is particularly preferable to use a release paper). When a release PET film or release paper is used, the release treatment or the resin layer may be formed on only one side of the film or paper or on both sides.
The thickness of the support film [II] is preferably 5 μm or more, particularly preferably 10 to 200 μm, more preferably 20 to 100 μm.

In the laminated film for fiber adhesion and / or fiber sheet surface protection of the present invention, the protective film [III] is laminated on the side of the thermosetting composition layer [I] on which the support film [II] is not laminated. May be.
The protective film [III] is used for the purpose of preventing the transfer of the adhesive thermosetting composition layer [I] to the support film [II] when the laminated film of the present invention is rolled. Examples of the protective film [III] used include polyethylene film, release PET film, polypropylene film, polyvinyl alcohol film, ethylene vinyl alcohol copolymer film, polytetrafluoroethylene film, and nylon. Although a film, a release paper, etc. are mentioned, A release PET film and a release paper are especially preferable.
The thickness of the protective film [III] is preferably 5 μm or more, particularly preferably 10 to 200 μm, more preferably 15 to 100 μm.

  As a method for producing the laminated film of the present invention, for example, an oven in which the thermosetting composition [i] is uniformly applied to one side of the support film [II] and the temperature is usually increased to 50 to 120 ° C. or sequentially. In general, there may be mentioned a method of forming the thermosetting composition layer [I] by drying for 1 to 60 minutes. Moreover, when using protective film [III], the method of forming the said thermosetting composition layer [I] and then carrying out pressure lamination of protective film [III] on the upper surface of this layer [I] is mentioned. .

In the laminated film of the present invention, when used for bonding fibers or protecting the surface of a fiber sheet, the thickness of the thermosetting composition layer [I] is preferably 50 μm or more, particularly 80 to 500 μm, more preferably 100 to 300 μm. Is preferred.
In the laminated film of the present invention, when design properties are imparted to the cured layer [I] obtained by curing the thermosetting composition layer [I], the thickness of the thermosetting composition layer [I] is 100 μm or more. In particular, 150 to 500 μm, more preferably 250 to 300 μm.
When the thickness of the thermosetting composition layer [I] is too thin, the number of layers to be laminated increases in order to obtain an appropriate thickness for adhering fibers or protecting the surface of the fiber sheet, and the lamination process becomes complicated. Or the cost tends to be too high, or it may be difficult to obtain a suitable thickness for adhesion or surface protection. Moreover, when this thickness is too thick, it tends to take too much time when the thermosetting composition [i] is dried to form the thermosetting composition layer [I].

The laminated film of the present invention thus obtained can be used for the adhesion of fibers such as carbon fibers and glass fibers and the protection of the surface of the fiber sheet composed of such fibers.
Examples of the fibers in the present invention include reinforcing fibers such as glass fibers, carbon fibers, aramid fibers, boron fibers, alumina fibers, and silicon carbide fibers. These fibers may be used in combination of two or more. In order to obtain a molded product that is lighter and more durable, glass fibers and carbon fibers are preferably used.
The form and arrangement of the fiber sheet are not particularly limited, and examples thereof include a sheet in which a bundle of fibers is aligned in one direction, a woven fabric (cross), a mat, a knit, and a non-woven fabric.

A method for producing a prepreg by using the laminated film of the present invention or the thermosetting composition for fiber bonding and / or fiber sheet surface protection of the present invention will be exemplarily outlined.
As a method for producing a prepreg using the laminated film of the present invention, for example, a fiber sheet and a laminated film are laminated, the support film [II] of the laminated film is peeled off, and another laminated film is used as a fiber as necessary. A method in which the fiber sheet is impregnated with the thermosetting composition [i] by heating and pressing after further laminating on the sheet or the thermosetting composition layer [I] and peeling off the support film [II] can be mentioned. Examples of the heating and pressurizing method include press molding, autoclave molding, and internal pressure molding.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to a following example, unless the summary is exceeded.
In the examples, “%” and “parts” mean weight basis.
The following were prepared as each component.

<Binder polymer (A)>
(A1-1): Polymethyl methacrylate (Mitsubishi Rayon “Dianar BR-83”)

<Reactive oligomer (B) having one or more unsaturated groups>
The following bifunctional urethane acrylate-based reactive oligomer (B1) was prepared as the reactive oligomer (B1).
(B1): In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port, isophorone diisocyanate 30.6 g (0.138 mol), bifunctional polyester polyol (hydroxyl value 145 mg KOH / g, number average) Molecular weight 800) 53.2 g (0.069 mol), 2,6-di-tert-butylcresol 0.04 g as a polymerization inhibitor, and dibutyltin dilaurate 0.02 g as a reaction catalyst were charged and reacted at 70 ° C. for 6 hours. Charge 16.2 g (0.140 mol) of 2-hydroxyethyl acrylate, react at 60 ° C. for 3 hours, and terminate the reaction when the residual isocyanate group becomes 0.1%. Bifunctional urethane acrylate reactivity Oligomer (B1) (weight average molecular weight 5,600, viscosity at 60 ° C. 56,000 m a · s) was obtained.

<Thermal polymerization initiator (C)>
(C1): 1,1′-di (t-hexylperoxy) cyclohexane (“Perhexa HC” manufactured by NOF Corporation) (10-hour half-life temperature: 87.1 ° C.)
(C2): t-butylbenzoyl peroxide (“Perbutyl Z” manufactured by NOF Corporation) (10-hour half-life temperature: 104.3 ° C.)
(C ′): Dilauroyl peroxide (“Parroyl L” manufactured by NOF Corporation) (10 hour half-life temperature: 61.6 ° C.)

<Reactive monomer (D) having one or more unsaturated groups>
(D1): Polyethylene glycol diacrylate (“A-200” manufactured by Shin-Nakamura Chemical Co., Ltd.)

[Example 1]
The resin solution obtained by diluting the binder polymer (A1-1) with ethyl acetate to 40% and the oligomer solution obtained by diluting the reactive oligomer (B1) with 2-butanone to 75% are reacted with the binder polymer (A1-1). The functional oligomer (B1) was mixed so that the weight ratio of nonvolatile components was 44:56. Furthermore, the reactive monomer (D1) was mixed so as to be 20 parts with respect to 100 parts in total of the nonvolatile content of the binder polymer (A1-1) and the reactive oligomer (B1).
Next, the thermal polymerization initiator (C1) is mixed so that the nonvolatile content of the mixture of (A1-1), (B1), and (D1) is 2 parts with respect to 100 parts of the nonvolatile content, and the nonvolatile content concentration is 60%. The resulting thermosetting composition [i-1] solution was obtained.
This thermosetting composition [i-1] solution was applied onto a 30 μm thick polyester film [II] using an applicator with a gap of 0.35 mm, and this was applied at 60 ° C. for 3 minutes and further at 80 ° C. for 3 minutes. By drying for a minute, a thermosetting composition layer [I-1] having a thickness of 100 μm was formed, and a laminated film for fiber bonding (E1) (hereinafter also simply referred to as “laminated film”) was obtained.
The obtained laminated film for fiber bonding (E1) was evaluated as follows.

(Adhesiveness of fiber sheet)
Two glass fiber sheets (“HG300” manufactured by Unitika Ltd., 100 mm × 15 mm size, thickness 270 μm) are prepared, and a thermosetting composition of a laminated film for fiber bonding (E1) on one glass fiber sheet The thermosetting resin layer [I-1] is formed on the glass fiber sheet by laminating the surface of the layer [I-1] and peeling off the polyester film [II], and the thermosetting composition. On the layer [I-1], the surface of the thermosetting composition layer [I-1] of the second laminated film for fiber bonding (E1) was bonded again to peel off the polyester film [II]. The remaining one glass fiber sheet is provided on the second thermosetting composition layer [I-1], and a 200 μm thermosetting composition layer [I-1] is provided between the two glass fiber sheets. Formed. The laminated body was cured while being impregnated into the glass fiber sheets on both sides by applying pressure of 4.2 MPa with a press machine heated to 150 ° C. and performing pressing for 1 minute. The two glass fiber sheets were bonded together. Thereafter, a 180 ° peel test was performed, and the two glass fiber sheets were not peeled off at a stress of 9 N / 15 mm, and showed strong adhesiveness.

[Example 2]
In Example 1, it carried out similarly except having changed the thermal-polymerization initiator (C1) into (C2), and obtained the laminated | multilayer film (E2). Evaluation similar to Example 1 was performed using the obtained laminated film for fiber bonding (E2).
As a result, when a 180 ° peel test was performed, the two glass fiber sheets were not peeled off at a stress of 9 N / 15 mm, and showed strong adhesion.

[Comparative Example 1]
In Example 1, it carried out similarly except having changed the thermal-polymerization initiator (C1) into (C '), and obtained the laminated | multilayer film (E'). Evaluation similar to Example 1 was performed using the obtained laminated film for fiber bonding (E ′).
As a result, when a 180 ° peel test was performed, two glass fiber sheets were peeled off at a stress of 9 N / 15 mm, and strong adhesion was not obtained.

  From the above results, it is possible to easily perform the resin penetration into the fiber sheet and thermosetting by laminating the fiber sheet on the laminated film for fiber adhesion and / or fiber sheet surface protection of the present invention and performing a heat press treatment. It was shown that it was possible. That is, the laminated film of the present invention was excellent in workability and productivity and excellent in the adhesiveness of the fiber sheet. Moreover, since the laminated film of the present invention is bonded and heat-cured, the surface of the fiber becomes smooth and excellent in surface smoothness, so that the design formability is also excellent.

Claims (8)

A laminated film for fiber adhesion and / or fiber sheet surface protection comprising a layer [I] comprising a thermosetting composition [i] and a support film [II],
The laminated film for fiber adhesion and / or fiber sheet surface protection, wherein the thermosetting composition [i] contains a thermal polymerization initiator (C) having a 10-hour half-life temperature of 65 ° C or higher.   2. The fiber bond and / or the fiber adhesive according to claim 1, wherein the thermosetting composition [i] further contains a binder polymer (A) and a reactive oligomer (B) having at least one unsaturated group. Laminated film for protecting fiber sheet surface.   The laminated film for fiber adhesion and / or fiber sheet surface protection according to claim 2, wherein the binder polymer (A) is a (meth) acrylic resin (A1).   The thermal polymerization initiator (C) having a 10-hour half-life temperature of 65 ° C. or higher is an azobis compound having a 10-hour half-temperature of 65 ° C. or higher or a peroxide compound having a 10-hour half-temperature of 65 ° C. or higher. The laminated film for fiber adhesion and / or fiber sheet surface protection according to any one of claims 1 to 3.   The fiber bonding and / or fiber according to any one of claims 1 to 4, wherein the thermosetting composition [i] further contains a reactive monomer (D) having one or more unsaturated groups. Laminated film for sheet surface protection.   The laminated film for fiber adhesion and / or fiber sheet surface protection according to any one of claims 1 to 5, wherein the thickness of the layer [I] comprising the thermosetting composition [i] is 50 µm or more.   Furthermore, protective film [III] is laminated | stacked on the side by which the support film [II] of the layer [I] which consists of thermosetting compositions [i] is not laminated | stacked, Any one of Claims 1-6 characterized by the above-mentioned. A laminated film for fiber adhesion and / or fiber sheet surface protection.   A fiber bond comprising a binder polymer (A), a reactive oligomer (B) having one or more unsaturated groups, and a thermal polymerization initiator (C) having a 10-hour half-life temperature of 65 ° C. or higher. And / or a thermosetting composition for protecting a fiber sheet surface.